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4-Bromo-3-methylbenzoic acid is a chemical compound with the formula C8H7BrO2, characterized by a white crystalline solid appearance. It features a benzoic acid molecule with a bromo group and a methyl group attached, which endows it with unique chemical properties and reactivity. 4-Bromo-3-methylbenzoic acid is a versatile intermediate in the synthesis of pharmaceuticals and organic compounds, playing a crucial role in the production of various drugs and organic synthesis processes.

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  • 7697-28-1 Structure
  • Basic information

    1. Product Name: 4-Bromo-3-methylbenzoic acid
    2. Synonyms: 4-BROMO-M-TOLUIC ACID;4-BROMO-3-METHYLBENZOIC ACID;3-methyl-4-bromobenzoic acid;RARECHEM AL BO 1293;4-Bromo-3-methyl;4-Bromo-3-methylbenz;2-Bromo-5-carboxytoluene, 4-Bromo-m-toluic acid;3 - Methyl - 4 - broMine benzoic acid
    3. CAS NO:7697-28-1
    4. Molecular Formula: C8H7BrO2
    5. Molecular Weight: 215.04
    6. EINECS: 231-713-7
    7. Product Categories: blocks;Bromides;Carboxes;Aromatic Carboxylic Acids, Amides, Anilides, Anhydrides & Salts;Benzoic acid;Organic acids;Acids & Esters;Bromine Compounds;C8;Carbonyl Compounds;Carboxylic Acids
    8. Mol File: 7697-28-1.mol
  • Chemical Properties

    1. Melting Point: 212-216 °C(lit.)
    2. Boiling Point: 311.4 °C at 760 mmHg
    3. Flash Point: 142.1 °C
    4. Appearance: Yellow to orange to tan/Powder
    5. Density: 1.599 g/cm3
    6. Vapor Pressure: 0.000243mmHg at 25°C
    7. Refractive Index: N/A
    8. Storage Temp.: Sealed in dry,Room Temperature
    9. Solubility: N/A
    10. PKA: 4.04±0.10(Predicted)
    11. BRN: 2356649
    12. CAS DataBase Reference: 4-Bromo-3-methylbenzoic acid(CAS DataBase Reference)
    13. NIST Chemistry Reference: 4-Bromo-3-methylbenzoic acid(7697-28-1)
    14. EPA Substance Registry System: 4-Bromo-3-methylbenzoic acid(7697-28-1)
  • Safety Data

    1. Hazard Codes: Xi
    2. Statements: 36/37/38
    3. Safety Statements: 26-36-37
    4. WGK Germany: 3
    5. RTECS:
    6. HazardClass: IRRITANT
    7. PackingGroup: N/A
    8. Hazardous Substances Data: 7697-28-1(Hazardous Substances Data)

7697-28-1 Usage

Uses

Used in Pharmaceutical Industry:
4-Bromo-3-methylbenzoic acid is used as a key intermediate for the synthesis of various drugs, contributing to the development of new medications and therapeutic agents. Its unique structure allows it to be a building block in the creation of complex organic molecules with potential medicinal properties.
Used in Organic Synthesis:
In the field of organic synthesis, 4-Bromo-3-methylbenzoic acid serves as a valuable reagent, facilitating the formation of a wide range of organic compounds. Its ability to undergo various chemical reactions makes it an essential component in the synthesis of complex organic molecules for research and industrial applications.
Used in Chemical Industry:
4-Bromo-3-methylbenzoic acid is utilized in the chemical industry for the production of various compounds, including those with applications in different sectors such as agriculture, materials science, and specialty chemicals. Its versatility and reactivity in chemical reactions make it a sought-after compound for the synthesis of a diverse array of products.

Check Digit Verification of cas no

The CAS Registry Mumber 7697-28-1 includes 7 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 4 digits, 7,6,9 and 7 respectively; the second part has 2 digits, 2 and 8 respectively.
Calculate Digit Verification of CAS Registry Number 7697-28:
(6*7)+(5*6)+(4*9)+(3*7)+(2*2)+(1*8)=141
141 % 10 = 1
So 7697-28-1 is a valid CAS Registry Number.
InChI:InChI=1/C8H7BrO2/c1-5-4-6(8(10)11)2-3-7(5)9/h2-4H,1H3,(H,10,11)/p-1

7697-28-1 Well-known Company Product Price

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  • Alfa Aesar

  • (A14302)  4-Bromo-3-methylbenzoic acid, 98%   

  • 7697-28-1

  • 1g

  • 204.0CNY

  • Detail
  • Alfa Aesar

  • (A14302)  4-Bromo-3-methylbenzoic acid, 98%   

  • 7697-28-1

  • 5g

  • 487.0CNY

  • Detail
  • Alfa Aesar

  • (A14302)  4-Bromo-3-methylbenzoic acid, 98%   

  • 7697-28-1

  • 25g

  • 1686.0CNY

  • Detail

7697-28-1SDS

SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 12, 2017

Revision Date: Aug 12, 2017

1.Identification

1.1 GHS Product identifier

Product name 4-Bromo-3-methylbenzoic acid

1.2 Other means of identification

Product number -
Other names 3-methyl-4-bromo-benzoic acid

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only.
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:7697-28-1 SDS

7697-28-1Synthetic route

4-amino 3-methylbenzoic acid
2486-70-6

4-amino 3-methylbenzoic acid

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
Stage #1: 4-amino 3-methylbenzoic acid With hydrogen bromide In water at 25℃; for 1h;
Stage #2: With sodium nitrate In water at -2 - -1℃; for 1.75h;
Stage #3: With hydrogen bromide; copper(I) bromide In water at -2 - 70℃; for 2h;
90%
Diazotization.Kochen der Diazoverbindung mit Bromwasserstoffsaeure;
With hydrogen bromide; sodium nitrite; copper(I) chloride In water
4,4'-dibromo-5,3'-dimethyl-2-nitrodiphenylmethane
84797-77-3

4,4'-dibromo-5,3'-dimethyl-2-nitrodiphenylmethane

A

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

B

6-bromo-5-methyl-3-(4'-bromo-3'-methylphenyl)-2,1-isoxazole
93099-47-9

6-bromo-5-methyl-3-(4'-bromo-3'-methylphenyl)-2,1-isoxazole

C

3,6-dibromo-2,7-dimethylacridone
84658-94-6

3,6-dibromo-2,7-dimethylacridone

Conditions
ConditionsYield
With sulfuric acid In ethanol for 5h; Irradiation;A 63%
B 20%
C 6%
With sulfuric acid In ethanol for 5h; Product distribution; Mechanism; Irradiation;A 51%
B 20%
C 6%
4-bromo-3-methyl-N-(2-methyl-4-cyanophenyl)benzamide
146308-26-1

4-bromo-3-methyl-N-(2-methyl-4-cyanophenyl)benzamide

A

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

B

4-amino-3-methylbenzonitrile
78881-21-7

4-amino-3-methylbenzonitrile

Conditions
ConditionsYield
With potassium hydroxide In ethanol a) 70 deg C, 4.5 h, b) 80 deg C, 3 h; Yields of byproduct given;A 63%
B n/a
With potassium hydroxide In ethanol a) 70 deg C, 4.5 h, b) 80 deg C, 3 h; Yield given;A 63%
B n/a
1-bromo-2,4-dimethylbenzene
583-70-0

1-bromo-2,4-dimethylbenzene

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
With nitric acid60%
With nitric acid for 24h; Heating / reflux;60%
With nitric acid at 150℃;
With nitric acid
n-butyllithium
109-72-8, 29786-93-4

n-butyllithium

1,4-dibromo-2-methylbenzene
615-59-8

1,4-dibromo-2-methylbenzene

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
With diethyl ether Aufgiessen des Reaktionsgemisches auf festes Kohlendioxid;
1,4-dibromo-2-methylbenzene
615-59-8

1,4-dibromo-2-methylbenzene

A

2-methylterephthalic acid
5156-01-4

2-methylterephthalic acid

B

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
With n-butyllithium; Petroleum ether anschliessendes Behandeln mit festem Kohlendioxid;
1-bromo-4-isopropyl-2-methyl-benzene
92243-75-9

1-bromo-4-isopropyl-2-methyl-benzene

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
With nitric acid
1-(4-bromo-3-methylphenyl)ethan-1-one
37074-40-1

1-(4-bromo-3-methylphenyl)ethan-1-one

A

4-bromo-isophthalic acid
6939-93-1

4-bromo-isophthalic acid

B

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
With potassium permanganate
With alkaline potassium permanganate
m-Toluic acid
99-04-7

m-Toluic acid

A

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

B

2-bromo-5-methylbenzoic acid
6967-82-4

2-bromo-5-methylbenzoic acid

Conditions
ConditionsYield
With bromine
amino-5-bromo-2-toluene
6933-10-4

amino-5-bromo-2-toluene

copper(I) cyanide
544-92-3

copper(I) cyanide

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
(i) NaNO2, aq. HCl, (ii) /BRN= 3587244/, (iii) NaOH, EtOH; Multistep reaction;
bromine
7726-95-6

bromine

m-Toluic acid
99-04-7

m-Toluic acid

A

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

B

2-bromo-5-methylbenzoic acid
6967-82-4

2-bromo-5-methylbenzoic acid

n-butyllithium
109-72-8, 29786-93-4

n-butyllithium

1,4-dibromo-2-methylbenzene
615-59-8

1,4-dibromo-2-methylbenzene

petroleum ether

petroleum ether

A

4-bromo-2-methylbenzoic acid
68837-59-2

4-bromo-2-methylbenzoic acid

B

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
at 20℃; anschliessend Behandlung mit CO2;
1-bromo-2,4-dimethylbenzene
583-70-0

1-bromo-2,4-dimethylbenzene

chromic acid mixture

chromic acid mixture

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-ethyl-1-bromo-2-methyl-benzene
90560-90-0

4-ethyl-1-bromo-2-methyl-benzene

nitric acid
7697-37-2

nitric acid

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

1-bromo-4-isopropyl-2-methyl-benzene
92243-75-9

1-bromo-4-isopropyl-2-methyl-benzene

nitric acid
7697-37-2

nitric acid

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

asymm. bromo-m-xylene

asymm. bromo-m-xylene

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
With dichromate mixture
1-(4-bromo-3-methylphenyl)ethan-1-one
37074-40-1

1-(4-bromo-3-methylphenyl)ethan-1-one

KMnO4

KMnO4

aqueous KOH

aqueous KOH

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-Bromobenzoic acid
586-76-5

4-Bromobenzoic acid

methyl iodide
74-88-4

methyl iodide

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
Stage #1: 4-Bromobenzoic acid With 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran; hexane at -78℃; for 4h;
Stage #2: methyl iodide In tetrahydrofuran; hexane at -78 - 20℃;
12 % Spectr.
3-Methylacetanilide
537-92-8

3-Methylacetanilide

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
Multi-step reaction with 2 steps
1: (i) (bromination), (ii) (hydrolysis)
2: (i) NaNO2, aq. HCl, (ii) /BRN= 3587244/, (iii) NaOH, EtOH
View Scheme
4-Bromo-3-methylbenzoic acid methyl ester
148547-19-7

4-Bromo-3-methylbenzoic acid methyl ester

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

Conditions
ConditionsYield
Stage #1: 4-Bromo-3-methylbenzoic acid methyl ester With water; sodium hydroxide In tetrahydrofuran at 20℃; for 16h;
Stage #2: With hydrogenchloride In water
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-bromo-3-methylbenzylalcohol
149104-89-2

4-bromo-3-methylbenzylalcohol

Conditions
ConditionsYield
With borane-THF In tetrahydrofuran at 0 - 20℃;100%
With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 0.25h;100%
With borane In tetrahydrofuran at -30 - 20℃;98%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

phenylboronic acid
98-80-6

phenylboronic acid

2-methyl[1,1'-biphenyl]-4-carboxylic acid
178313-67-2

2-methyl[1,1'-biphenyl]-4-carboxylic acid

Conditions
ConditionsYield
With disodium hydrogenphosphate; disodium bis(2-aminopyrimidine-4,6-diolate)palladium acetate In water at 50 - 120℃; for 0.166667h; Microwave irradiation;100%
With disodium hydrogenphosphate; Pd(OAc)2(2-amino-4,6-dihydroxypyrimidine disodium salt)2 In water at 120℃; for 0.166667h; Suzuki-Miyaura coupling; Microwave irradiation;99%
With potassium fluoride; palladium diacetate; XPhos In tetrahydrofuran for 1h; Heating / reflux;
3-METHOXYBENZYLAMINE
5071-96-5

3-METHOXYBENZYLAMINE

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-bromo-N-(3-methoxybenzyl)-3-methylbenzamide
1623120-19-3

4-bromo-N-(3-methoxybenzyl)-3-methylbenzamide

Conditions
ConditionsYield
With N-ethyl-N,N-diisopropylamine; HATU In dichloromethane at 20℃; for 1h; Inert atmosphere;100%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

m-tolylboronic acid
17933-03-8

m-tolylboronic acid

3-methyl-4-(m-tolyl)benzoic acid

3-methyl-4-(m-tolyl)benzoic acid

Conditions
ConditionsYield
With disodium hydrogenphosphate; disodium bis(2-aminopyrimidine-4,6-diolate)palladium acetate In water at 50 - 120℃; for 0.166667h; Microwave irradiation;100%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

isopropylamine
75-31-0

isopropylamine

4-bromo-N-isopropyl-3-methylbenzamide

4-bromo-N-isopropyl-3-methylbenzamide

Conditions
ConditionsYield
With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate at 0 - 20℃; for 1h;100%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

2-Methylphenylboronic acid
16419-60-6

2-Methylphenylboronic acid

2,2’-dimethyl-1,1’-biphenyl-4-carboxylic acid
69535-85-9

2,2’-dimethyl-1,1’-biphenyl-4-carboxylic acid

Conditions
ConditionsYield
With disodium hydrogenphosphate; Pd(OAc)2(2-amino-4,6-dihydroxypyrimidine disodium salt)2 In water at 120℃; for 0.166667h; Suzuki-Miyaura coupling; Microwave irradiation;99%
With disodium hydrogenphosphate; disodium bis(2-aminopyrimidine-4,6-diolate)palladium acetate In water at 50 - 120℃; for 0.166667h; Microwave irradiation;95%
3-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-yl)aniline
1428155-06-9

3-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-yl)aniline

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-bromo-3-methyl-N-(3-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-yl)phenyl)benzamide
1428155-45-6

4-bromo-3-methyl-N-(3-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-yl)phenyl)benzamide

Conditions
ConditionsYield
With N-ethyl-N,N-diisopropylamine; HATU In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere;99%
methanol
67-56-1

methanol

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-Bromo-3-methylbenzoic acid methyl ester
148547-19-7

4-Bromo-3-methylbenzoic acid methyl ester

Conditions
ConditionsYield
With sulfuric acid In methanol for 14h; Reflux;97%
With sulfuric acid Reflux;95%
Stage #1: methanol With acetyl chloride for 0.416667h;
Stage #2: 4-bromo-3-methylbenzoic acid for 18h; Heating / reflux;
93%
ethanol
64-17-5

ethanol

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

ethyl 3-methyl-4-bromobenzoate
160313-69-9

ethyl 3-methyl-4-bromobenzoate

Conditions
ConditionsYield
With thionyl chloride at 83℃; for 6h;96%
With sulfuric acid In toluene for 1h; Heating;80%
With hydrogenchloride
N-trimethylsilylmethylamine
18166-02-4

N-trimethylsilylmethylamine

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-bromo-3-methyl-N-trimethylsilanylmethyl-benzamide
1370257-42-3

4-bromo-3-methyl-N-trimethylsilanylmethyl-benzamide

Conditions
ConditionsYield
Stage #1: 4-bromo-3-methylbenzoic acid With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 0.5h;
Stage #2: N-trimethylsilylmethylamine In dichloromethane at 20℃; Product distribution / selectivity;
94%
cyclobutylamine
2516-34-9

cyclobutylamine

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-bromo-N-cyclobutyl-3-methylbenzamide

4-bromo-N-cyclobutyl-3-methylbenzamide

Conditions
ConditionsYield
With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃;94%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

methylamine
74-89-5

methylamine

4-bromo-N,3-dimethylbenzamide

4-bromo-N,3-dimethylbenzamide

Conditions
ConditionsYield
Stage #1: 4-bromo-3-methylbenzoic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2h;
Stage #2: methylamine In ethanol at 20℃; for 0.5h;
94%
2-(2-Hydroxyethyl)pyridine
103-74-2

2-(2-Hydroxyethyl)pyridine

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

2-(2-pyridyl)ethyl 4-bromo-3-methylbenzoate
920270-48-0

2-(2-pyridyl)ethyl 4-bromo-3-methylbenzoate

Conditions
ConditionsYield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 16h; Inert atmosphere;92%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

3-(8-nitroquinolin-4-yl)benzenamine

3-(8-nitroquinolin-4-yl)benzenamine

4-bromo-3-methyl-N-(3-(8-nitroquinolin-4-yl)phenyl)benzamide

4-bromo-3-methyl-N-(3-(8-nitroquinolin-4-yl)phenyl)benzamide

Conditions
ConditionsYield
With N-ethyl-N,N-diisopropylamine; HATU In N,N-dimethyl-formamide at 0 - 20℃;92%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-carboxyphenylboronic acid
14047-29-1

4-carboxyphenylboronic acid

2-methyl-[1,1′-biphenyl]-4,4′-dicarboxylic acid
1186048-28-1

2-methyl-[1,1′-biphenyl]-4,4′-dicarboxylic acid

Conditions
ConditionsYield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; triphenylphosphine In water; N,N-dimethyl-formamide at 90℃; for 24h;91%
With {1,1'-bis(diphenylphosphino)ferrocene} palladium dibromide; sodium carbonate In water; N,N-dimethyl-formamide at 90℃; for 3h; Inert atmosphere;
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene for 24h; Reflux;
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-phenyl-2,3-dihydro-1H-indole
179473-53-1

4-phenyl-2,3-dihydro-1H-indole

(4-bromo-3-methylphenyl)(4-phenylindolin-1-yl)methanone

(4-bromo-3-methylphenyl)(4-phenylindolin-1-yl)methanone

Conditions
ConditionsYield
Stage #1: 4-bromo-3-methylbenzoic acid; 4-phenyl-2,3-dihydro-1H-indole With N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃;
Stage #2: With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 2h;
90.2%
With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃; for 3h;87%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

bis(pinacol)diborane
73183-34-3

bis(pinacol)diborane

3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid
269409-74-7

3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic acid

Conditions
ConditionsYield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In N,N-dimethyl-formamide at 120℃; for 0.25h; Microwave irradiation;90%
With potassium acetate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In N,N-dimethyl-formamide at 120℃; for 0.25h; Microwave irradiation;90%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide at 125℃; for 0.333333h; Microwave irradiation;74%
With triethylamine; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In 1,4-dioxane at 20 - 80℃;
di-tert-butyl dicarbonate
24424-99-5

di-tert-butyl dicarbonate

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

tert-butyl 4-bromo-3-methylbenzoate
347174-28-1

tert-butyl 4-bromo-3-methylbenzoate

Conditions
ConditionsYield
With dmap In tetrahydrofuran Reflux;87%
With dmap In tetrahydrofuran Reflux;87%
With dmap In tetrahydrofuran; tert-butyl alcohol at 70℃; for 12h; Inert atmosphere;70%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

1-bromo-2-methyl-4-(trifluoromethyl)benzene
929000-62-4

1-bromo-2-methyl-4-(trifluoromethyl)benzene

Conditions
ConditionsYield
With sulfur tetrafluoride; hydrogen fluoride at 85℃; for 24h; Autoclave; Inert atmosphere;87%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

potassium tert-butylate
865-47-4

potassium tert-butylate

tert-butyl 4-bromo-3-methylbenzoate
347174-28-1

tert-butyl 4-bromo-3-methylbenzoate

Conditions
ConditionsYield
Stage #1: 4-bromo-3-methylbenzoic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2.33333h;
Stage #2: potassium tert-butylate In tetrahydrofuran at 0 - 20℃; for 1h;
86%
Stage #1: 4-bromo-3-methylbenzoic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane for 2h; Inert atmosphere;
Stage #2: potassium tert-butylate In tetrahydrofuran at 0 - 20℃; for 2h;
69%
Stage #1: 4-bromo-3-methylbenzoic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 4h; Inert atmosphere;
Stage #2: potassium tert-butylate In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere;
42%
Stage #1: 4-bromo-3-methylbenzoic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2h;
Stage #2: potassium tert-butylate In tetrahydrofuran at 20℃; for 0.5h;
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-bromo-3-(bromomethyl)benzoic acid
887757-31-5

4-bromo-3-(bromomethyl)benzoic acid

Conditions
ConditionsYield
With 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 72h; Concentration; Reflux;86%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane at 76℃; for 72h;86%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 48h; Reflux;86%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)indoline

4-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)indoline

C24H20BrNO3

C24H20BrNO3

Conditions
ConditionsYield
Stage #1: 4-bromo-3-methylbenzoic acid; 4-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)indoline With N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃;
Stage #2: With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 3h;
85.5%
oxalyl dichloride
79-37-8

oxalyl dichloride

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

tert-butyl 4-bromo-3-methylbenzoate
347174-28-1

tert-butyl 4-bromo-3-methylbenzoate

Conditions
ConditionsYield
With potassium tert-butylate In tetrahydrofuran; N-methyl-acetamide; dichloromethane; water85%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

potassium phenyltrifluoborate

potassium phenyltrifluoborate

C14H11BrO2

C14H11BrO2

Conditions
ConditionsYield
With dipotassium hydrogenphosphate; oxygen; palladium diacetate; p-benzoquinone In tert-butyl alcohol at 100℃; under 22801.5 Torr; for 24h; regioselective reaction;85%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

methyl iodide
74-88-4

methyl iodide

4-Bromo-3-methylbenzoic acid methyl ester
148547-19-7

4-Bromo-3-methylbenzoic acid methyl ester

Conditions
ConditionsYield
With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 2.5h;83.1%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

dimethyl amine
124-40-3

dimethyl amine

4-bromo-N,N,3-trimethylbenzamide

4-bromo-N,N,3-trimethylbenzamide

Conditions
ConditionsYield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In tetrahydrofuran; dichloromethane at 20℃; for 16h;83%
With 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride In ethanol; water at 20℃; for 24h;65%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

{2‐azabicyclo[2.1.1]hexan‐1‐yl}methanamine

{2‐azabicyclo[2.1.1]hexan‐1‐yl}methanamine

N‐({2‐benzyl‐2‐azabicyclo[2.1.1]hexan‐1‐yl}methyl)‐4‐bromo‐3‐methylbenzamide

N‐({2‐benzyl‐2‐azabicyclo[2.1.1]hexan‐1‐yl}methyl)‐4‐bromo‐3‐methylbenzamide

Conditions
ConditionsYield
Stage #1: 4-bromo-3-methylbenzoic acid With 1-[(1-(cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylamino-morpholino)]-uronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 0.5h;
Stage #2: {2‐azabicyclo[2.1.1]hexan‐1‐yl}methanamine In dichloromethane at 20℃; for 1h;
82%
2-fluoro-N1-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-yl)benzene-1,4-diamine
1428155-04-7

2-fluoro-N1-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-yl)benzene-1,4-diamine

4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

4-bromo-N-(3-fluoro-4-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-ylamino)phenyl)-3-methylbenzamide
1428155-17-2

4-bromo-N-(3-fluoro-4-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-ylamino)phenyl)-3-methylbenzamide

Conditions
ConditionsYield
With N-ethyl-N,N-diisopropylamine; HATU In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere;80%
4-bromo-3-methylbenzoic acid
7697-28-1

4-bromo-3-methylbenzoic acid

methyl 6-aminocaproate hydrochloride
1926-80-3

methyl 6-aminocaproate hydrochloride

methyl 6-(4-bromo-3-methylbenzamido)hexanoate
1255952-05-6

methyl 6-(4-bromo-3-methylbenzamido)hexanoate

Conditions
ConditionsYield
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; trimethylamine In dichloromethane for 20h; Inert atmosphere;78%

7697-28-1Relevant articles and documents

ORGANIC COMPOUNDS

-

Page/Page column 53-54, (2011/04/14)

The present invention provides compounds of the following structure; [in-line-formulae]A-L1-B-C-D[/in-line-formulae] that are useful for treating or preventing conditions or disorders associated with DGAT1 activity in animals, particularly humans.

2,3,4,5-TETRAHYDRO-1H-1,5-BENZODIAZEPINE DERIVATIVE AND MEDICINAL COMPOSITION

-

, (2008/06/13)

The present invention has its object to provide a 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivative represented with the Formula (1) , or the pharmaceutically acceptable salt, which is effective as a therapeutic and prophylactic agent for diabetes, diabetic nephropathy, or glomerulosclerosis.

FUSED TRICYCLIC COMPOUNDS AS INHIBITORS OF TUMOR NECROSIS FACTOR-ALPHA

-

Page/Page column 54, (2010/11/30)

Compounds of formula (1): are disclosed, wherein V is CH2; W is S(O)m; m is the integer 0, 1 or 2; U is O, C(O), CR13R14 or NR15; where R13 is H, alkyl; R14 is H, OH, OR13 or OCOR13; R15 is H, alkyl, cycloalkyl, alkenyl, C(O)R13, C(O)OR13 or alkylaminocarbonyl; R1, R2, R3, R4, R5, R6, R7 and R8 are as defined herein. These compounds are inhibitor of tumor necrosis factor-alpha (TNF- ) and are useful as medicaments for the treatment and prevention of disorders caused by increased TNF- activity, in particular inflammations.

2,3,4,5-TETRAHYDRO-1H-1,5-BENZODIAZEPINE DERIVATIVE AND MEDICINAL COMPOSITION

-

Page/Page column 64-65, (2010/11/30)

A 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivative represented by the generalformula (1): [Chemical formula 1] (1) or a pharmaceutically acceptable saltthereof. They are useful as a therapeutic/preventive agent for diabetes, diabeticnephropathy, or glomerulosclerosis.

The first regioselective metalation and functionalization of unprotected 4-halobenzoic acids

Gohier, Frederic,Castanet, Anne-Sophie,Mortier, Jacques

, p. 1501 - 1504 (2007/10/03)

(Chemical Equation Presented) By treatment with s-BuLi, s-BuLi/TMEDA, or t-BuLi at ~-78°C, 4-fluoro- and 4-chlorobenzoic acids (1a,b) are metalated preferentially in the position adjacent to the carboxylate. A complete reversal in regioselectivity is observed for 1a when treated with LTMP; a sequential process involving a rapid intraaggregate lithiation through a quasi dianion complex "QUADAC" is postulated to explain the unusual reactivity of Me2S2 and I2.

CONDENSED PYRAZOLE DERIVATIVES, METHOD OF MANUFACTURING THE SAME, AND ANDROGEN INHIBITOR

-

, (2008/06/13)

This invention provides a condensed pyrazole derivative of the Formula (1): STR1 (where A denotes CH or N, R 0 and R 3 denote same or different, a hydrogen atom or a lower alkyl group, R 1 and R 2 denote same or different, a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a nitro group or a halogen atom, m denotes 1 or 2, and n denotes 1, 2 or 3, provided that, when n is 2, two R 2 may be connected to each other to form a lower alkylenedioxy group), or its pharmaceutically acceptable salt. This derivative or its salt is excellent in the effect of inhibiting the expression of action of androgen, thereby being excellent in therapeutical effect of benign prostatic hypertrophy, prostatic carcinoma, etc., and has a long lasting of efficacy and high oral absorption.

The Synthesis of Pyridocarbazoles from Diphenylamine Derivatives: Alternative Routes to and Relay Syntheses of Ellipticines and Olivacines

Hall, Robin J.,Marchant, Jeremy,Oliveira-Campos, Ana M. F.,Queiroz, Maria-Joao R. P.,Shannon, Patrick V. R.

, p. 3439 - 3450 (2007/10/02)

Two new synthetic routes to pyridocarbazoles are described.In the first, Goldberg-type coupling of various aryl sulfonamides with aryl bromides in the presence of copper and potassium carbonate gives N,N-diaryl sulfonamides.UV irradiation of these, in ethanol, removes the toluene-p-sulfonyl protecting groups and cyclises the diphenylamine moiety to the corresponding carbazoles.These carbazoles are established intermediates in the synthesis of several ellipticines (5,11-dimethylpyridocarbazoles).In a complementary route, a series of substituted acetanilides are similarly coupled under Goldberg conditions with 2-bromo-5-cyanotoluene to give the corresponding cyanodiphenylamines and diphenylamides.Hydrolysis of the latter gives the diphenylamines which are then oxidatively cyclised to 3-cyano-1-methylcarbazoles.Reduction of the cyanocarbazoles leads to 3-formylcarbazoles which are known intermediates for the synthesis of 5-methylpyridocarbazoles.

Photolyis of 2-Nitrodiphenylmethanes in Isopropanol and Acidified Aqueous Ethanol

Christudhas, M.,Jacob, E. Dominic,Joshua, C. P.

, p. 815 - 817 (2007/10/02)

2-Nitrodiphenylmethane (1a) on irradiation in isopropanol and acidified ethanol yields benzoic acids as the major product. 3-Phenyl-2,1-benzisoxazole (2a) and acridone (3a) are also formed, though in lower yields. 4,4'-Dichloro/bromo-5,5'-dimethyl-2-nitrodiphenylmethanes (1b, c) on similar irradiation yields 4-halo-3-methylbezoic acid (4) as the major product. 5-Methyl-4-halo-3-(4'-halo-3'-methylphenyl)-2,1-benzisoxazole (2b, c) and acridones (3b, c) are also formed.A plausible mechanism for the formation of various products in the photoreactions is discussed.

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